A process for fabricating slightly Cu-poor thin-films of Cu(In,Ga)Se.sub.2 on a substrate for semiconductor device applications includes the steps of forming initially a slightly Cu-rich, phase separated, mixture of Cu(In,Ga)Se.sub.2 :Cu.sub.x Se on the substrate in solid form followed by exposure of the Cu(In,Ga)Se.sub.2 :Cu.sub.x Se solid mixture to an overpressure of Se vapor and (In,Ga) vapor for deposition on the Cu(In,Ga)Se.sub.2 :Cu.sub.x Se solid mixture while simultaneously increasing the temperature of the solid mixture toward a recrystallization temperature (about 550.degree. C.) at which Cu(In,Ga)Se.sub.2 is solid and Cu.sub.x Se is liquid. The (In,Ga) flux is terminated while the Se overpressure flux and the recrystallization temperature are maintained to recrystallize the Cu.sub.x Se with the (In, Ga) that was deposited during the temperature transition and with the Se vapor to form the thin-film of slightly Cu-poor Cu.sub.x (In,Ga).sub.y Se.sub.z. The initial Cu-rich, phase separated large grain mixture of Cu(In,Ga)Se.sub.2 :Cu.sub.x Se can be made by sequentially depositing or co-depositing the metal precursors, Cu and (In, Ga), on the substrate at room temperature, ramping up the thin-film temperature in the presence of Se overpressure to a moderate anneal temperature (about 450.degree. C.) and holding that temperature and the Se overpressure formore » an annealing period. A nonselenizing, low temperature anneal at about 100.degree. C. can also be used to homogenize the precursors on the substrates before the selenizing, moderate temperature anneal.« less

Enhanced quality thin films of Cu.sub.w (In,Ga.sub.y)Se.sub.z for semiconductor device applications are fabricated by initially forming a Cu-rich, phase-separated compound mixture comprising Cu(In,Ga):Cu.sub.x Se on a substrate to form a large-grain precursor and then converting the excess Cu.sub.x Se to Cu(In,Ga)Se.sub.2 by exposing it to an activity of In and/or Ga, either in vapor In and/or Ga form or in solid (In,Ga).sub.y Se.sub.z. Alternatively, the conversion can be made by sequential deposition of In and/or Ga and Se onto the phase-separated precursor. The conversion process is preferably performed in the temperature range of about 300.degree.-600.degree. C., where the Cu(In,Ga)Se.sub.2 remainsmore » solid, while the excess Cu.sub.x Se is in a liquid flux. The characteristic of the resulting Cu.sub.w (In,Ga).sub.y Se.sub.z can be controlled by the temperature. Higher temperatures, such as 500.degree.-600.degree. C., result in a nearly stoichiometric Cu(In,Ga)Se.sub.2, whereas lower temperatures, such as 300.degree.-400.degree. C., result in a more Cu-poor compound, such as the Cu.sub.z (In,Ga).sub.4 Se.sub.7 phase.« less

Enhanced quality thin films of Cu[sub w](In,Ga[sub y])Se[sub z] for semiconductor device applications are fabricated by initially forming a Cu-rich, phase-separated compound mixture comprising Cu(In,Ga):Cu[sub x]Se on a substrate to form a large-grain precursor and then converting the excess Cu[sub x]Se to Cu(In,Ga)Se[sub 2] by exposing it to an activity of In and/or Ga, either in vapor In and/or Ga form or in solid (In,Ga)[sub y]Se[sub z]. Alternatively, the conversion can be made by sequential deposition of In and/or Ga and Se onto the phase-separated precursor. The conversion process is preferably performed in the temperature range of about 300--600 C,more » where the Cu(In,Ga)Se[sub 2] remains solid, while the excess Cu[sub x]Se is in a liquid flux. The characteristic of the resulting Cu[sub w](In,Ga)[sub y]Se[sub z] can be controlled by the temperature. Higher temperatures, such as 500--600 C, result in a nearly stoichiometric Cu(In,Ga)Se[sub 2], whereas lower temperatures, such as 300--400 C, result in a more Cu-poor compound, such as the Cu[sub z](In,Ga)[sub 4]Se[sub 7] phase. 7 figs.« less

Systems and methods for forming solar cells with CuInSe.sub.2 and Cu(In,Ga)Se.sub.2 films are provided. In one embodiment, a method comprises: during a first stage (220), performing a mass transport through vapor transport of an indium chloride (InCl.sub.x) vapor (143, 223) and Se vapor (121, 225) to deposit a semiconductor film (212, 232, 252) upon a substrate (114, 210, 230, 250); heating the substrate (114, 210, 230, 250) and the semiconductor film to a desired temperature (112); during a second stage (240) following the first stage (220), performing a mass transport through vapor transport of a copper chloride (CuCl.sub.x) vapor (143,more » 243) and Se vapor (121, 245) to the semiconductor film (212, 232, 252); and during a third stage (260) following the second stage (240), performing a mass transport through vapor transport of an indium chloride (InCl.sub.x) vapor (143, 263) and Se vapor (121, 265) to the semiconductor film (212, 232, 252).« less

A method of fabricating spaced-apart back contacts on a thin film of semiconductor material by forming strips of buffer material on top of the semiconductor material in locations corresponding to the desired dividing lines between back contacts, forming a film of metal substantially covering the semiconductor material and buffer strips, and scribing portions of the metal film overlying the buffer strips with a laser without contacting the underlying semiconductor material to separate the metal layer into a plurality of back contacts. The buffer material serves to protect the underlying semiconductor material from being damaged during the laser scribing. Back contactsmore » and multi-cell photovoltaic modules incorporating such back contacts also are disclosed.« less

A process for producing a slightly Cu-poor thin film of Cu(In,Ga)(Se,S).sub.2 comprises depositing a first layer of (In,Ga).sub.x (Se,S).sub.y followed by depositing just enough Cu+(Se,S) or Cu.sub.x (Se,S) to produce the desired slightly Cu-poor material. In a variation, most, but not all, (about 90 to 99%) of the (In,Ga).sub.x (Se,S).sub.y is deposited first, followed by deposition of all the Cu+(Se,S) or Cu.sub.x (Se,S) to go near stoichiometric, possibly or even preferably slightly Cu-rich, and then in turn followed by deposition of the remainder (about 1 to 10%) of the (In,Ga).sub.x (Se,S).sub.y to end with a slightly Cu-poor composition. In yetmore » another variation, a small portion (about 1 to 10%) of the (In,Ga).sub.x (Se,S).sub.y is first deposited as a seed layer, followed by deposition of all of the Cu+(Se,S) or Cu.sub.x (Se,S) to make a very Cu-rich mixture, and then followed deposition of the remainder of the (In,Ga).sub.x (Se,S).sub.y to go slightly Cu-poor in the final Cu(In,Ga)(Se,S).sub.2 thin film.« less